Cosmetic Compositions Having Improved Transfer Resistance

ABSTRACT

Cosmetic compositions and methods with improved transfer resistance and long wear properties are disclosed. The cosmetic compositions contain a synergistic combination of at least one silicone polyurethane polymer and at least one elastomer.

FIELD OF INVENTION

The present invention relates generally to long wearing, transferresistance cosmetics such as lipstick, mascara and the like.

BACKGROUND OF THE INVENTION

Many cosmetics and personal care products employ various film formingagents to aid in spreading and adhering a formulation to a surface suchas skin. The class of polymers known as organosiloxanes, includingpolydimethylsiloxane (PDMS or Dimethicone), have recently receivedconsiderable attention as film-formers in cosmetic products due to theirexcellent spreading properties and biological inertness. Examples ofcosmetic formulations including organosiloxane film formers include, forexample, U.S. Pat. No. 6,780,402 (L'Oreal), U.S. Pat. No. 5,318,775(Mary Kay Cosmetics), U.S. Pat. No. 4,699,780 (Estee Lauder); and U.S.Pat. No. 4,578,266 (Revlon), the disclosures of which are herebyincorporated by reference. Recent advances have included the use ofpolyorganosiloxane polyurethane polymers.

For example, U.S. Patent Publication No. 2005/0238611 describes cosmeticcompositions comprising a particular silicone polyurethane which is thereaction product of a silicone pre-polymer with a diisocyanate. Thesilicone pre-polymer is an alkoxylated, bis-hydroxyalkyl groupterminated polydialkylsiloxane, in which the reactive —OH group isattached to a carbon atom. It is stated that the use of the particularsilicone-containing polyurethane provides improved film-formingproperties and imparts transfer-resistance.

U.S. Pat. No. 6,166,093 describes polyurethane block condensationproducts comprising a polysiloxane graft and their use as film-formersin treating keratinous materials.

U.S. Pat. No. 5,643,581 describes cosmetic compositions comprising apseudolatex based on a multiblock polycondensate which contains apolysiloxane block and a polyurethane and/or polyurea block wherein thepolyurethane and/or polyurea block further comprises anionic or cationicgroups.

U.S. Pat. No. 6,120,753 describes skin cleansing compositions, said tohave moisturizing properties, which comprise a urethane siloxanecopolymer.

Despite the advances in film forming methods and compositions, thereremains a need in the art for improved transfer resistance and long wearproperties for cosmetic compositions for the skin and hair.

It is therefore an object of the invention to provide compositions andmethods for improved transfer resistance and long wear properties forcosmetic compositions for the skin and hair.

SUMMARY OF INVENTION

In accordance with the foregoing objectives and others, the presentinvention provides cosmetic compositions which are resistant totransfer, durable, and comfortable to wear. More particularly, theinvention relates to cosmetic compositions containing at least onesilicone polyurethane polymer in combination with at least oneelastomer, typically in a suitable cosmetic vehicle. Compositionsaccording to the invention may be applied to the skin, including thelips, or hair, including eyelashes, eyebrows, hairs of the scalp and thelike. The composition impart a durable film resistant to transfer uponcontact with objects such as clothing, napkins, etc.

In one aspect of the invention, long-wearing, transfer resistantcosmetic compositions for application to the skin or hair are provided.Such compositions provide a durable deposit upon the skin or hair thatresists degradation over time. The cosmetic compositions will typicallycomprise: (i) at least one silicone polyurethane polymer; and (ii) atleast one elastomer; wherein the weight ratio of silicone polyurethanepolymer to elastomer is from about 50:1 to about 1:50, typically, fromabout 10:1 to about 1:10, and preferably from about 5:1 to 1:5. The atleast one elastomer will preferably be selected from the groupconsisting of silicone gums, polyisobutylene, natural rubbers, andblock-copolymer rubbers.

In another aspect of the invention, long-wearing, transfer resistantcosmetic compositions are provided comprising: (i) at least one siliconepolyurethane polymer; and (ii) at least one elastomer selected from thegroup consisting of silicone gums, polyisobutylene, natural rubbers, andblock-copolymer rubbers; wherein the weight ratio of siliconepolyurethane polymer to elastomer is from about 50:1 to about 1:50;wherein the composition provides a improvement in at least onecharacteristic selected from the groups consisting of water transferresistance, oil transfer resistance, flexibility, storage modulus (G′),loss modulus (G″) and/or loss tangent (tan(δ)). Preferably, theimprovement in at least one characteristic will include an improvementin water transfer resistance and/or oil transfer resistance, morepreferably a synergistic improvement in water transfer resistance and/oroil transfer resistance.

In a further aspect of the invention, the cosmetic compositions willcomprise:

-   -   (1) at least one silicone polyurethane polymer which is the        reaction product of:        -   (a) an hydroxyl functionalized polydimethylsiloxane of the            form:

where L is a bond or a linker group selected from divalent C₁₋₁₀hydrocarbons; and n is an integer from 0 to 5,000 and,

-   -   -   (b) a diisocyante of the form O═C═N—R¹—N═C═O, where R¹ is a            divalent moiety selected from the groups consisting of:            -   (i) a group of the form:

-   -   -   -   (ii) a group of the form:

-   -   -   -   (iii) a group of the form:

-   -   -   -   (iv) a group of the form:

and;

-   -   -   -   (v) a group of the form:

and combinations thereof; and

-   -   (2) at least one elastomer selected from the group consisting of        silicone gums, polyisobutylene, natural rubbers, and        block-copolymer rubbers; and    -   (3) a cosmetically acceptable vehicle,        wherein the silicone polyurethane polymer and elastomer are        present in a weight ratio from about 50:1 to about 1:50; and        wherein said composition provides a synergistic improvement in        water transfer resistance.

In another aspect of the invention, a method is provided for formingtransfer resistant and/or long-wearing film on skin or keratin fiberscomprising applying a composition according to the invention to skin orkeratin fibers, wherein the composition comprises a synergisticcombination of a silicone polyurethane polymer and an elastomer. Theresultant film is expected to have improved durability and/or transferresistance on skin or keratin fibers for a long-wear period such as fromabout 1 to about 24 hours, as compared to an otherwise identicalcomposition which does not comprise the synergistic combination.

In one variant according to this aspect of the invention, a method forimparting a transfer resistant and/or long wearing film to skin orkeratin fibers is provided comprising applying to the skin or keratinfibers a cosmetic or personal care composition comprising, in a suitablevehicle, a synergistic combination of:

-   -   a) at least one silicone polyurethane polymer; and    -   b) at least one polyorganosiloxane gum having a viscosity of        from about 500,000 cst to about 5,000,000 cst at 25 degrees        Celsius; wherein said synergistic combination comprises a weight        ratio from about 50:1 to about 1:50 of the at least one silicone        polyurethane polymer to the at least one polyorganosiloxane gum.

In yet another aspect of the invention, a method for imparting atransfer resistant and/or long wearing film to the skin or keratinfibers is provided comprising applying to skin or keratin fibers acosmetic or personal care composition comprising, in a suitable vehicle,a synergistic combination of:

-   -   a) at least one silicone polyurethane polymer; and    -   b) at least one polyisobutylene elastomer; wherein said        synergistic combination comprises a weight ratio from about 50:1        to about 1:50 of the at least one silicone polyurethane polymer        to the at least one polyorganosiloxane gum.

These and other aspects of the present invention will become apparent tothose skilled in the art after a reading of the following detaileddescription of the invention, including the illustrative embodiments andexamples.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the water transfer resistance of exemplary tip glossformulations as a function of the percentage by weight of siliconepolyurethane polymer.

FIG. 1 illustrates the water transfer resistance of lip glossformulations comprising silicone polyurethane in the absence of anelastomer (♦) as a function of the amount of silicone polyurethane (byweight %) compared to the water transfer resistance of lip glossformulations comprising varying concentrations of silicone polyurethanein combination with 6 weight % silicone gum elastomer (▪), and a tipgloss formulation comprising silicone polyurethane in combination with12% by weight silicone gum (▴).

FIG. 2 illustrates the oil transfer resistance of lip gloss formulationscomprising silicone polyurethane in the absence of an elastomer (♦) as afunction of the amount of silicone polyurethane (by weight %) comparedto the oil transfer resistance of lip gloss formulations comprisingvarying concentrations of silicone polyurethane in combination with 6weight % silicone gum elastomer (▪), and a lip gloss formulationcomprising silicone polyurethane in combination with 12% by weightsilicone gum (▴).

FIG. 3 illustrates the combined oil and water transfer resistance of lipgloss formulations comprising silicone polyurethane in the absence of anelastomer (♦) as a function of the amount of silicone polyurethane (byweight %) compared to the combined oil and water transfer resistance oflip gloss formulations comprising varying concentrations of siliconepolyurethane in combination with 6 weight % silicone gum elastomer (▪),and a lip gloss formulation comprising silicone polyurethane incombination with 12% by weight silicone gum (▴).

FIG. 4 shows the storage modulus (G′) as a function of shear rate for: asilicone polyurethane polymer (A); a silicone gum elastomer (B); apolyisobutylene elastomer (C); a synergistic combination of siliconepolyurethane polymer and silicone gum elastomer (D); and a synergisticcombination of silicone polyurethane polymer and polyisobutyleneelastomer (E).

FIG. 5 shows the loss tangent (tan δ) as a function of shear rate for: asilicone polyurethane polymer (A); a silicone gum elastomer (B); apolyisobutylene elastomer (C); a synergistic combination of siliconepolyurethane polymer and silicone gum elastomer (D); and a synergisticcombination of silicone polyurethane and polyisobutylene elastomer (E).

FIG. 6 shows the storage modulus (G′) as a function of shear rate forlip gloss formulations of Sample 1 of Example II and Samples 21-25 ofExample VI.

FIG. 7 shows the loss tangent (tan δ) as a function of shear rate ininverse seconds for lip gloss formulations of Sample 1 of Example II andSamples 21-25 of Example VI.

DETAILED DESCRIPTION

The present invention is founded on the discover that combinations ofcertain silicone polyurethane polymers and elastomers provide asynergistic result in their long wearing, transfer resistant propertiesfor cosmetic compositions when applied to biological surfaces. As usedherein, the term “biological surface” is meant to include any surface towhich cosmetic and personal care products are applied, including withoutlimitation, skin (including lips), hair (including eyelashes, eyebrowsor hairs of the scalp), and nails.

The composition generally comprise a silicone polyurethane polymers incombination with a elastomer. The combination of these componentsprovides a synergistic improvement in transfer resistance of thecosmetic. By “synergistic improvement” is meant that the combination ofsilicone polyurethane polymer and elastomer improves one or morecharacteristics of the cosmetic as compared to otherwise identicalcompositions lacking either the silicone polyurethane polymer or theelastomer. The improvement may manifest in a variety characteristics,but typically will relate to the viscoelastic properties of the appliedfilm. The viscoelasticity of the cosmetic film provides substantivity tothe skin and thus will contribute to long-wear, flexibility, andtransfer resistance to both oily and watery substrates. The viscoelasticproperties may be quantified on the basis of storage modulus G′, lossmodulus G″, and loss tangent tan (δ) which is the ratio of G″/G′. Thus,the synergistic improvement may be an improvement in one or morecharacteristics selected from length of wear, flexibility, watertransfer resistance, oil transfer resistance, and rheology, by which ismeant an improvement in the viscoelasticity of one or more of storagemodulus G′, loss modulus G″, and toss tangent tan (δ), or anycombination thereof. In a preferred embodiment, the compositions willexhibit a synergistic improvement in transfer resistance, particularlywater transfer resistance.

The inventive compositions are contemplated to be synergistic over anyrange of relative proportions of polyorganosiloxane gum to elastomerbased on the observation that cosmetic properties are enhanced due tothe combination of a viscous component and an elastic component.Typically, the ratio of silicone polyurethane polymer topolyorganosiloxane gum ranges from about 50:1 to about 1:50, moretypically from about 25:1 to about 1:25, and usually from about 10:1 toabout 1:10. The synergistic combinations are expected to have their mostpronounced effects of the viscoelastic properties of the cosmeticcompositions when they are present in a weight ratio of siliconepolyurethane polymer to polyorganosiloxane gum from about 5:1 to about1:5, preferably about 3:1 to about 1:3, and more preferred still fromabout 2:1 to about 1:2, including a weight ratio of siliconepolyurethane polymer to polyorganosiloxane gum of about 1:1.

An essential component of the inventive compositions is a siliconepolyurethane polymer. In the broadest sense of the invention, theselection of the silicone polyurethane polymer is not particularlylimited and will embrace any polymer comprising organosiloxane units andurethane linkages.

In one embodiment, the silicone polyurethane polymer will be thereaction product of a hydroxyl functionalized polyorganosiloxane,preferably containing two or more hydroxyl groups, with a diisocyantatemoiety. The hydroxyl functionalized polyorganosiloxane will typicallyhave the structure of Formula I:

where R is selected independently at each occurrence from hydrogen,hydroxyl, and optionally substituted hydrocarbon groups containing from1 to 10 carbon atoms, and in particular from optionally substitutedalkyl, alkenyl, alkynyl, aryl, alkyl-aryl, or aryl-alkyl groups;preferably R is selected from optionally substituted branched, straightchain, or cyclic C₁₋₆ alkyl or alkenyl groups, including withoutlimitation, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl,amyl, hexyl, cyclohexyl, vinyl, allyl, and the like or C₁₋₈ aryl,alkyl-aryl, or aryl-alkyl groups, including without limitation, phenyl,benzyl, tolyl, xylyl and the like;

wherein each of the foregoing R groups may include optional substitutionby one or more heteroatoms, including oxygen, nitrogen, phosphorous, andhalogen, particularly fluorine, as exemplified by fluoroalkyl (includingperfluoroalkyl) groups, such as mono-, di-, and tri-fluoromethyl,perfluorophenyl, and the like, amino-substituted C₁₋₆ alkyl groups,including those having the form —(CH₂)₁₋₆—NR^(N) ₂ and—(CH₂)₁₋₆—NR^(N)—(CH₂)₁₋₆—NR^(N) ₂ where R^(N) is typically hydrogen,but may be methyl, ethyl, propyl, and the like; polyether groupsincluding without limitation, polyethyleneoxide groups of the form—(CH₂CH₂O)_(n)—, polypropylene oxide groups of the form—(CH(CH₃)CH₂O)_(n)— and combinations thereof; and amine oxide,phosphate, hydroxyl, ester, and/or carboxylate functionalities, and thelike; or wherein R may comprise an additional group —L—OH;

wherein L either represents a bond or a linker group; preferably L is alinker group selected from divalent hydrocarbons having from 1 to 10carbon atoms, including divalent alkyl, alkenyl, alkynyl, aryl,alkyl-aryl, or aryl-alkyl groups, as exemplified by C₁₋₁₀ alkyl groups,including without limitation, divalent groups of the form —(CH₂)₁₋₁₀—,preferably —(CH₂)₁₋₆—, and more preferably, L is —CH₂CH₂CH₂—;

and where n is an integer from 0 to 5,000, preferably from 1 to 200,more preferably from 10 to 100, and more preferred still from 10 to 50.Preferably R represents at least one or more occurrences of methyl, morepreferably, R represents methyl at all or substantially all by which ismeant that R represents methyl at greater than 90%, 95% or 98%occurrences.

In one embodiment according to the invention, the hydroxylfunctionalized polyorganosiloxane comprises a polymethylsiloxane, andsuitable has the structure of Formula Ia:

where L and n are as defined previously. In a preferred embodiment ofthe invention, the hydroxyl functionalized polyorganosiloxane comprisesa polymethylsiloxane, and suitable has the structure of Formula Ib:

where n is as defined above.

The diisocyanate will be of the form O═C═N—R¹—N═C═O, where R¹ is adivalent hydrocarbon group containing from 1 to 20 carbon atoms,including optional substitution with one or more heteroatoms, and inparticular R¹ will be selected from optionally substituted, branched,straight chain, or cyclic alkyl, alkenyl, alkynyl, aryl, alkyl-aryl, oraryl-alkyl groups; including without limitation:

-   -   (i) a group of the form:

-   -   (ii) a group of the form:

-   -   (ii) a group of the form:

-   -   (iv) a group of the form:

-   -   and;    -   (v) a group of the form:

and combinations thereof.

Suitable diisocyanates include, without limitation, toluenediisocyanate; methylene diphenyl diisocyanate, including 2,2′-MDI,2,4′-MDI, and 4,4′-MDI; 1,6-hexamethylene diisocyanate; isophoronediisocyanate; methylene dicyclohexyl diisocyanate; xylene diisocyanate;cyclohexane diisocyanate; 3,3′-dimethyl-4,4′-diphenylmethanediisocyanate; p-phenylene diisocyanate; m-phenylene diisocyanate;4,4′-isopropylidene dicyclohexyl isocyanate; and the like. In apreferred embodiment, the diisocyanate is selected from the groupconsisting of 1,6-hexamethylene diisocyanate, methylene dicyclohexyldiisocyanate, isophorone diisocyanate, and combinations thereof. In oneembodiment, the diisocyanate will comprise, consist essentially of orconsist of 1,6-hexamethylene diisocyanate. In another embodiment, thediisocyanate will comprise, consist essentially of, or consist ofisophorone diisocyanate. In yet another embodiment, the diisocyanatewill comprise, consist essentially of, or consist of methylenedicyclohexyl diisocyanate.

The polyorganosiloxane polyurethane polymer will comprise repeat unitsderived from the hydroxyl functionalized polyorganosiloxane and thediisocyanate in the form of an AB alternating copolymer, where unit Ahas the structure of Formula II:

where R, L, and n are as defined previously in relation to Formula I,Ia, and Ib, and where unit B has the structure of Formula III:

where R¹ is as defined previously, and wherein units A and B arearranged in a linear, branched, or cyclic configuration.

When the polymer is a cyclic polymer, it may be represented according toFormula IV:

where z is an integer value from 2 to 2,000. Where thepolyorganosiloxane polyurethane polymer is cyclic, the propagation ofthe polymer is self-terminating. However, in the case of a linearpolymer, termination may be accomplished by, for example, allowing thepolymerization reaction to run to completion, employing a stoichiometricexcess of dihydroxyl polyorganosiloxane of Formula I in relation todiisocyanate, quenching the reaction with a mono-alcohol or an amine,for example a dialkyl amine, including in the reaction mixturequantities of monofunctional reactants, such as mono-hydroxylpolyorganosiloxane analogs of Formula I, and/or mono-functionalisocyanate reactants, or any other suitable method for terminating theurethane polymerization reaction. Thus, the polyorganosiloxane polymersmay have a variety of terminating groups, including without limitation,hydroxyl groups, including the group —L—OH, tri-alkylsilyl groups,including trimethylsilyl, hydrocarbons, such as linear, branched orcyclic alkyl or aryl groups which may, amines, cabinol, silanols and thelike.

The polymer may also include branching or grafting points in thepolyorganosiloxane where one or more groups R Formula I or II is a groupsuch as:

where R is as defined for Formula I, and R* may represent a group —L—O—further coupling the side chain to a unit B of Formula III, which may inturn be further coupled to unit A of Formula II, and so on, or R* mayrepresent —L—OH, a group R, as defined previously, or a terminatinggroup. When the polyorganosiloxane comprises branch or graft points ofthis type, they may be present as T-type or Q-type branches or grafts,where denotes that only one group on a Si atom is a polyorganosiloxanechain as shown above and Q denotes that both geminal R groups arepolyorganosiloxanes. These types of polyorganosiloxane compounds arereferred to as T-resin or Q-resin, branched or grafted, co-polymer ofpolyorganosiloxane polyurethane.

The polyorganosiloxane polyurethane polymers may also be prepared fromfunctionalized isocyanate prepolymers. For example, an isocyanateprepolymer may be a di-functional or multi-functional polyorganosiloxaneisocyanate, such as the polyorganosiloxane diisocyanate shown below inFormula V:

where R, R¹, and L as defined previously and where x is an integer from0 to 5,000, preferably from 1 to 200, more preferably from 10 to 100,and more preferred still from 10 to 50. The prepolymer may bemulti-functional as well by introducing additional isocyanate-bearinggroups at one or more R groups. The isocyanate-functionalizedpolyorganosiloxane prepolymer is reacted with a hydroxyl-functionalizedpolyorganosiloxane prepolymer such as that according to Formula I or amulti-functional analog thereof. The prepolymer according to Formula Vwill typically have a molecular weight ranging from about 4,000 to about15,000 Daltons. The prepolymer according to Formulas I, Ia, and Ib willtypically have a molecular weight ranging from about 250 to about 15,000Daltons.

In one embodiment, the silicone polyurethane polymer free of or isessentially free of polyalkylene glycol subunits, including polyethyleneglycol (PEG) or polypropylene glycol (PPG) subunits. By “essentiallyfree of” is meant that the polymer comprises less than about 1% byweight, preferably, less than about 0.5% by weight, and more preferably,less than about 0.1% by weight polyalkylene glycol subunits.

In a currently preferred embodiment, the polyorganosiloxane polyurethanepolymer for use in the cosmetic compositions of the invention is acyclic polymer comprising the reaction product of Formula Ib with adiisocyanate selected from the group consisting of 1,6-hexamethylenediisocyanate, methylene dicyclohexyl diisocyanate, isophoronediisocyanate, and combinations thereof. An exemplary siliconepolyurethane polymer is available from Siltech Corporation under thedesignation MR-20-41. A variety of prepolymers of Formulas I, Ia, andIb, having varying molecular weights and degrees of functionality, arecommercially available from Siltech Corporation under the tradedesignations “Silmer OH.” A variety of prepolymers of Formula V, havingvarying molecular weights and degrees of functionality, are commerciallyavailable from Siltech Corporation under the trade designations “SilmerNCO.”

A second essential component of the inventive compositions is anelastomeric material, including without limitation silicone gums,polyisobutylene, natural rubbers, block-copolymer rubbers, and the like.There is essentially no restriction on the nature of the elastomer andany cosmetically suitable elastomer is contemplated to be useful in thepractice of the invention.

In one embodiment, the elastomeric material will comprise a siloxanegum, in particular a polyorganosiloxane gum. While it is contemplatedthat any polyorganosiloxane gum will be suitable in the practice of theinvention, the polyorganosiloxane gum will typically have the followinggeneral structure:

where R² is selected, independently at each occurrence, from optionallysubstituted hydrocarbon groups containing from 1 to 10 carbon atoms, andin particular from optionally substituted alkyl, alkenyl, alkynyl, aryl,alkyl-aryl, or aryl-alkyl groups; preferably R² is selected fromoptionally substituted branched, straight chain, or cyclic C₁₋₆ alkyl oralkenyl groups, including without limitation, methyl, ethyl, propyl,isopropyl, butyl, isobutyl, t-butyl, amyl, hexyl, cyclohexyl, vinyl,allyl, and the like or C₁₋₈ aryl, alkyl-aryl, or aryl-alkyl groups,including without limitation, phenyl, benzyl, tolyl, xylyl and the like;

wherein each of the foregoing groups R² may include optionalsubstitution by one or more heteroatoms, including oxygen, nitrogen,phosphorous, and halogen, particularly fluorine, as exemplified byfluoroalkyl (including perfluoroalkyl) groups, such as mono-, di-, andtri-fluoromethyl, perfluorophenyl and the like, amino-substituted C₁₋₆alkyl groups, including those having the form —(CH₂)₁₋₆—NR^(N) ₂ and—(CH₂)₁₋₆—NR^(N)—(CH₂)₁₋₆—NR^(N) ₂ where R^(N) is typically hydrogen,but may be methyl, ethyl, propyl, and the like; polyether groupsincluding without limitation, polyethyleneoxide groups of the form—(CH₂CH₂O)_(n)—, polypropylene oxide groups of the form—(CH(CH₃)CH₂O)_(n)— and combinations thereof; and amine oxide,phosphate, hydroxyl, ester, and/or carboxylate functionalities, and thelike;

and optionally wherein R², at one or more occurrences, may be a group:

thereby introducing one or more branching points into polyorganosiloxanegum;

and wherein R³ is selected, independently at each occurrence, fromhydrogen, hydroxyl, a group —R′, or a group —OR′; wherein R′ representsoptionally substituted hydrocarbon radical having from 1 to 10 carbonatoms, including without limitation alkyl, alkenyl, alkynyl, aryl,alkyl-aryl, or aryl-alkyl groups, and preferably R′ is a branched,straight chain, or cyclic C₁₋₆ alkyl group, including methyl, ethyl,propyl, isopropyl, butyl, t-butyl, amyl, hexyl, cyclohexyl and the like,optionally comprising one ore more heteroatoms, wherein each of theforegoing groups may include optional substitution by one or moreheteroatoms, including oxygen, nitrogen, and halogen, particularlyfluorine, as exemplified by fluoroalkyl (including perfluoroalkyl)groups, such as mono-, di-, and tri-fluoromethyl, perfluorophenyl, andthe like, and in the case where the one or more heteroatoms includenitrogen, R′ may be and amino-substituted C₁₋₆ alkyl group, includingthose having the form —(CH₂)₁₋₆—NR^(N) ₂ and—(CH₂)₁₋₆—NR^(N)—(CH₂)₁₋₆—NR^(N) ₂ where R^(N) is typically hydrogen,but may be methyl, ethyl, propyl, and the like;

and wherein n (and m if present) is an integer value selected to providea polymer having a viscosity of about 500,000 to about 5,000,000centistokes at 25° C.

In one embodiment, R² and R³ are selected from the group consisting ofmethyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, hexyl,and cyclohexyl, vinyl, allyl, phenyl, and combinations thereof. In apreferred embodiment all occurrences of R² and R³ are methyl groups andthe silicone gum is a polydimethylsiloxane (dimethicone). Arepresentative polydimethylsiloxane silicone gum has the structure shownin Formula VI:

The polyorganosiloxane elastomeric material may include combinations oflow molecular weight polymers (i.e., fluids), high molecular weightpolymers (i.e., gums), and highly cross-linked silicones (i.e., resins).Combinations of the foregoing are suitable provided that thepolyorganosiloxane material exhibit elastomeric propertiescharacteristic of gums, i.e., the G′ storage modulus does not break downover a wide range of shear rates. These properties are enhanced wherethe polyorganosiloxane gum has a viscosity of from about 1,000,000centistokes to about 3,500,000 centistokes when measure at 25° C. In arepresentative embodiment, the polyorganosiloxane gum has a viscosity ofabout 2,500,000 centistokes at 25° C., An example of suitablecommercially available polyorganosiloxane gum is SE63 dimethicone gumfrom GE Silicones.

Other elastomers found to be suitable for inclusion in the inventivecompositions include polyolefin polymer, including without limitation,polyisobutylenes. Polyisobutylenes may be prepared by cationicpolymerization of isobutylene and will comprise repeat units as shownbelow:

These polymers are preferably, but not necessarily, fully saturated toimpart chemical stability. Depending on the value of n, polyisobutylenesmay range from a liquid to a rubber as the molecular weight isincreased. At low molecular weight, such as below 5,000 Daltons thepolymers tend to be liquid and at higher molecular weight, for example,greater than 100,000 Daltons, they tend to be rubbers. One suitablepolyisobutylene is Permethyl 98B from Presperse, Inc. which case thechemical abstracts number CAS:9003-29-6.

The elastomer component may include a natural rubber such as the latexobtained from the Hevea brasiliensis tree. Such natural rubbers compriseprimarily cis-1,4-polyisoprene repeat units of the form:

These rubbers are typically characterized by a low glass transitiontemperature (T_(g)˜−70° C.) and a high shear storage plateau modulus.The molecular weight of these natural rubbers is very high, typicallygreater than 1,000,000 Daltons.

Synthetic rubbers are also contemplated to by useful elastomericcomponents. Synthetic rubbers include thermoplastic block copolymersrubbers such as ABA block copolymers where A is polystyrene block of theform and B is as polydiene, such as, for example, polyisoprene and/orpolybutadiene, as shown below:

In the case where R in unit B is hydrogen, the polydiene block is apolybutadiene and the resultant block co-polymer with polystyrene isreferred to in the art as an SBS copolymer. In the case where R ismethyl, the polydiene is polyisoprene and the block co-polymer withpolystyrene is referred to in the art as an SIS copolymer. The molecularweight of the block copolymers is typically on the order of 100,000 to200,000 Daltons. It is contemplated the SBS and SIS copolymers will besuitable elastomers for use in the inventive compositions. In thesepolymers, the polystyrene is typically present from about 10 to about20% by weight of the rubber. As the minor component, the polystyreneblock is believed to phase separate into microscopic spherical domainsthat act as cross-links at each end of a polydiene polymer chain. Thesepolystyrene component is typically glassy at room temperature(T_(g)˜100° C.) whereas the polydiene component is rubbery (T_(g)˜−70°C.). The interesting elastic properties of these block copolymersarising as a result of the polydiene chains being anchored in the glassypolystyrene domain, thus the block copolymers behave as cross-linkedrubbers. At temperatures above T_(g) of the polystyrene, the microscopicglassy domains melt allowing the polymer chains to flow, permittinghot-melt processing. All of those foregoing properties are expected toimpart unique rheological attributes to cosmetic formulations comprisingthese materials, and in particular they are contemplated to enhance theviscoelastic properties of the cosmetic in a synergistic manner incombination with a polyorganosiloxane polyurethane polymers. Suitableblock copolymers include, without limitation, those available from ShellChemical under the tradename Kraton™ adhesives.

The cosmetic compositions will typically comprise a cosmeticallyacceptable vehicle. By “cosmetically acceptable” is meant that thevehicle is safe for contact with human skin and the like. It iscontemplated that any cosmetically acceptable vehicle known in the artwill be useful. The vehicle may comprise water, hydrophobic, and/orhydrophilic solvents. Suitable hydrophilic solvents include but are notlimited to, butylene glycol, propylene glycol, pentylene glycol,caprytyl glycol, polyglycerol diisostearate, dimethylsiloxane/glycolcopolymer, isopropyl myristate, triisostearyl citrate, or anycombinations thereof. Suitable hydrophobic vehicles include hydrocarbonoils, which may be saturated or unsaturated, have an aliphatic characterand be straight or branched chained or contain alicyclic or aromaticrings. Examples of preferred non-polar, volatile hydrocarbons includepolydecanes such as isododecane and isodecane, including for example,Permethyl-99A (Presperse Inc.) and the C₇-C₈ through C₁₂-C₁₅isoparaffins such as the Isopar Series available from Exxon Chemicals. Arepresentative solvent is isododecane. Silicone oils are alsocontemplated to be suitable vehicles, including without limitationhexamethyldisiloxane (HMDS), polydimethylsiloxane (dimethicone)polymers, and cyclodimethicones. Suitable dimethicone polymers areavailable from Dow Coming under the name Dow Corning 200® Fluid and haveviscosities ranging from 0.65 to 600,000 centistokes. Suitablenon-polar, volatile liquid silicone oils are disclosed in U.S. Pat. No.4,781,917, herein incorporated by reference in its entirety. Additionalvolatile silicones materials are described in Todd et al., “VolatileSilicone Fluids for Cosmetics”, Cosmetics and Toiletries, 91:27-32(1976), herein incorporated by reference in its entirety. Linearvolatile silicones generally have a viscosity of less than about 5centistokes at 25° C., whereas the cyclic silicones have viscosities ofless than about 10 centistokes at 25° C. Examples of cyclomethicones ofvarying viscosities include Dow Corning 200, Dow Corning 244, DowCorning 245, Dow Corning 344, and Dow Coming 345, (Dow Coming Corp.);SF-1204 and SF-1202 Silicone Fluids (G.E. Silicones), GE 7207 and 7158(General Electric Co.); and SWS-03314 (SWS Silicones Corp.).Polyethersiloxane copolymers are also contemplated as useful vehiclesincluding, without limitation, polyoxyalkylene ether copolymers having aviscosity of about 1200 to 1500 centistokes at 25° C., including forexample SH1066 organosilicone surfactant (General Electric Company).

The combination of silicone polyurethane and elastomer will typicallycomprise from about 0.1% by weight to about 90% by weight of the totalcosmetic composition. More typically, the combination will compriseabout 1% by weight to about 60% by weight and preferably will comprisefrom about 5% by weight to about 50% by weight of the total cosmeticcomposition.

The carrier will typically comprise from about 5% to about 95% by weightof the composition, and more typically between about 30% and about 80%by weight. In preferred embodiments, the carrier comprises between about50% and about 70% by weight of the composition.

The compositions according to the invention may be useful in a varietyof cosmetic and personal care products, including without limitation,lipsticks, and lipcolors, lip gloss, mascaras, transfer-resistantfoundations, eyeliner, eyeshadow, water-proof sunscreens and insectrepellents, skin care products, hair care products, antiperspirants anddeodorants, and other cosmetic products where durable, transferresistant films are desired.

Where the product is a color cosmetic, such as a lipstick, lip gloss,nail enamel, mascara, foundation, and the like, the compositions willfurther comprise one or more coloring agents. It is within the skill inthe art to choose coloring agents and combinations of coloring agents toproduce a desired color. Suitable coloring agents, including pigments,lakes, and dyes, are well known in the art and are disclosed in theC.T.F.A. Cosmetic ingredient Handbook, First Edition, 1988, the contentsor which are hereby incorporated by reference. Organic pigments include,for example, FD&C dyes, D&C dyes, including D&C Red, Nos. 2, 5, 6, 7,10, 11, 12, 13, 30 and 34, D&C Yellow No. 5, Blue No. 1, Violet No. 2.Exemplary inorganic pigments include, but are not limited to, metaloxides and metal hydroxides such as magnesium oxide, magnesiumhydroxide, calcium oxide, calcium hydroxides, aluminum oxide, aluminumhydroxide, iron oxides (α-Fe₂O₃, y-Fe₂O₃, Fe₃O₄, FeO), red iron oxide,yellow iron oxide, black iron oxide, iron hydroxides, titanium dioxide,titanium lower oxides, zirconium oxides, chromium oxides, chromiumhydroxides, manganese oxides, cobalt oxides, cerium oxides, nickeloxides and zinc oxides and composite oxides and composite hydroxidessuch as iron titanate, cobalt titanate and cobalt aluminate. Othersuitable colorants include ultramarine blue sodium aluminum silicatecontaining sulfur), Prussian blue, manganese violet, bismuthoxychloride, talc, mica, sericite, magnesium carbonate, calciumcarbonate, magnesium silicate, aluminum magnesium silicate, silica,titanated mica, iron oxide titanated mica, bismuth oxychloride, and thelike. The colorants may be surface modified with, for example,fluoropolymers, to adjust one or more characteristics of the colorant asdescribed in, for example, U.S. Pat. Nos. 6,471,950, 5,482,547, and4,832,944, the contents of which are hereby incorporated by reference.Suitable pearling pigments include without limitation bismuthoxychloride, guanine and titanium composite materials containing, as atitanium component, titanium dioxide, titanium lower oxides or titaniumoxynitride, as disclosed in U.S. Pat. No. 5,340,569, the contents ofwhich are hereby incorporated by reference. The compositions may alsoinclude glittering agents.

Various fillers and additional components may be added. Suitable fillersinclude without limitation silica, treated silica, talc, zinc stearate,mica, kaolin, Nylon powders such as Orgasol™, polyethylene powder,Teflon™, starch, boron nitride, copolymer microspheres such as Expancel™(Nobel Industries), Polytrap™ (Dow Corning) and silicone resinmicrobeads (Tospearl™ from Toshiba), and the like. Functional agents maybe, for example, insect repellants, UV absorbers, UV blockers,antiperspirants, moisturizers, conditioners, tooth whiteners, and thelike.

Additional pigment/powder fillers include, but are not limited to,inorganic powders such as gums, chalk, Fuller's earth, kaolin, sericite,muscovite, phlogopite, synthetic mica, lepidolite, biotite, lithia mica,vermiculite, aluminum silicate, starch, smectite clays, alkyl and/ortrialkyl aryl ammonium smectites, chemically modified magnesium aluminumsilicate, organically modified montmorillonite clay, hydrated aluminumsilicate, fumed aluminum starch octenyl succinate barium silicate,calcium silicate, magnesium silicate, strontium silicate, metaltungstate, magnesium, silica alumina, zeolite, barium sulfate, calcinedcalcium sulfate (calcined gypsum), calcium phosphate, fluorine apatite,hydroxyapatite, ceramic powder, metallic soap (zinc stearate, magnesiumstearate, zinc myristate, calcium palmitate, and aluminum stearate),colloidal silicone dioxide, and boron nitride; organic powder such aspolyamide resin powder (nylon powder), cyclodextrin, methylpolymethacrylate powder, copolymer powder of styrene and acrylic acid,benzoguanamine resin powder, polyethylene tetrafluoride) powder, andcarboxyvinyl polymer, cellulose powder such as hydroxyethyl celluloseand sodium carboxymethyl cellulose, ethylene glycol monostearate;inorganic white pigments such as magnesium oxide; andstabilizers/rheology modifiers, for example, Bentone Gel and RheopearlTT2. Other useful powders are disclosed in U.S. Pat. No. 5,688,831, thedisclosure of which is hereby incorporated by reference.

In another embodiment, the invention is formulated in a conventionallipstick or lipcolor product. Such conventional lip products include,without limitation, U.S. Pat. Nos. 6,509,009, 6,428,797, 6,261,576,5,747,017, 5,318,775, and 4,935,228, the disclosures of which are herebyincorporated by reference.

The compositions according to the invention may include viscositymodifying materials, structuring agents, synthetic or natural waxes,film-forming agents, preservatives, stabilizing agents, flavors, andfragrances. The compositions of the invention may optionally compriseother active and inactive ingredients typically associated with any ofthe foregoing cosmetic and personal care products, including, but notlimited to, excipients, fillers, emulsifying agents, antioxidants,surfactants, film formers, chelating agents, gelling agents, thickeners,emollients, humectants, moisturizers, vitamins, minerals, viscosityand/or rheology modifiers, sunscreens, keratolytics, depigmentingagents, retinoids, hormonal compounds, alpha-hydroxy acids, alpha-ketoacids, anti-mycobacterial agents, antifungal agents, antimicrobials,antivirals, analgesics, lipidic compounds, anti-allergenic agents, H1 orH2 antihistamines, anti-inflammatory agents, anti-irritants,antineoplastics, immune system boosting agents, immune systemsuppressing agents, anti-acne agents, anesthetics, antiseptics, insectrepellents, skin cooling compounds, skin protectants, skin penetrationenhancers, exfollients, lubricants, fragrances, colorants, stainingagents, depigmenting agents, hypopigmenting agents, preservatives,stabilizers, pharmaceutical agents, photostabilizing agents, andmixtures thereof. In addition to the foregoing, the personal careproducts of the invention may contain any other compound for thetreatment of skin disorders.

The composition according to the invention is expected to achieveimproved durability and/or transfer resistance and remain on the skin orhair for a long-wear period such as from about 1 to about 24 hours. Thecomposition is also expected to maintain transfer resistance and/orlong-wear properties for a long-wear period such as from about 1 hour toabout 24 hours. Typically, a long-wear period may be from about 8 toabout 24 hours. Preferably, the long-wear period may be from about 8 toabout 12 hours. An alternative preferred long-wear period may be fromabout 12 to about 24 hours.

A variety of evaluation methods of transfer resistance and long wearingproperties are known in the cosmetic arts, such as in dry blot, oilblot, and rub tests. For example, U.S. Pat. No. 6,071,503 disclosesvarious methods of evaluating cosmetic properties, the disclosure ofwhich is hereby incorporated by reference.

Improved Cosmetic Properties

The combination of a silicone polyurethane polymer and an elastomer in acosmetic formulation provides synergistic results in cosmeticproperties, particularly, substantivity or adhesive strength, of thecosmetic formulation to a selected surface. The flow and deformationbehaviors of the lip gloss formulation directly affects its longwearing, transfer resistant properties. The polyorganosiloxanepolyurethane polymers are, by nature, viscous materials whereaselastomers are, by definition, highly elastic. The synergisticcombination of the present invention includes an elastic component fromthe elastomers to balance the viscosity of the polyorganosiloxanepolyurethane polymer. As discussed below, it is believed that balancedviscoelasticity of the lip gloss formulation provides improvedsubstantivity to the skin and thus will contribute to long-wear,flexibility, and transfer resistance of the lip gloss formulation underboth oily and watery conditions.

Balanced viscoelastic properties are expected to improve transferresistance and provide good substantivity to the lip gloss formulation.Increased elasticity provide for improved transfer resistance of the lipgloss formulation, but as the elasticity increases, the polymeric chainsof the material becomes more entangled resulting in a loss of adhesionto the surface, Viscosity is related to the glass transition temperature(T_(g)) of a material through the well-known Williams-Landel-Ferry (WLF)equation. As viscosity increases, the glass transition temperature(T_(g)) also increases. An increase in the glass transition temperature(T_(g)) results in a more brittle cosmetic product, particularly whereT_(g) is above temperatures typically encountered by a cosmetic product(e.g., room temperature or body temperature). A decreased viscosityprovides a lower glass transition temperature (T_(g)) and a moreadhesive, but more transferable material at temperatures typicallyencountered by a cosmetic product. The viscoelastic properties may bequantified on the basis of storage modulus G′, loss modulus G″, and losstangent tan (δ) which is the ratio of G″/G′.

In general, a material can respond to shear force by (1) storingrecoverable elastic energy or (2) dissipating unrecoverable viscousloss. The storage modulus (G′) quantifies elastic behavior and revealsthe ability of the polymer system to store elastic energy associatedwith recoverable elastic deformation while the loss modulus (G″)measures the dynamic viscous behavior that relates to the dissipation ofenergy associated with unrecoverable viscous loss. The loss tangent (tanδ), which is the ratio of the loss modulus to the storage modulus,compares the ratio of energy lost to energy stored in a cycle ofdeformation and provides a comparative parameter that combines both theelastic and the viscous contributions the system (i.e.,viscoelasticity). The relationship between G′, G″ and tan δ is:

${\tan \; \delta} = \frac{G^{\prime\prime}}{G^{\prime}}$

Lip gloss formulations typically encounter low levels of shear forcesduring wear. It would be particularly desirable to impart improvedtransfer resistance and good substantivity to lip gloss formulations atshear rates typically experienced during wear, such as from about 0.1 toabout 1 sec⁻¹. Preferably, the lip gloss formulations may demonstrateimproved transfer resistance and good substantivity at shear rates fromabout 0.1 to about 2.5 sec⁻¹. More preferably, the lip glossformulations may demonstrate improved transfer resistance and goodsubstantivity at shear rates from about 0.1 to about 5 sec⁻¹. Even morepreferably, the lip gloss formulations may demonstrate improved transferresistance and good substantivity at shear rates from about 0.1 to about10 sec⁻¹. Most preferably, the lip gloss formulations may demonstrateimproved transfer resistance and good substantivity at shear rates fromabout 0.1 to about 15 sec⁻¹.

Lip gloss formulations typically encounter higher levels of shear stressduring application to the skin. At higher shear rates, it isparticularly preferable that the lip gloss formulation becomes moredeformable so that a consumer may readily apply and spread the lip glossformulation to cover a selected surface. Accordingly, it is particularlydesirable for the lip gloss formulation to become more viscous at shearrates typically encountered during application to the skin, for example,shear rates from about 1 sec⁻¹ to about 100 sec⁻¹. Preferably, the lipgloss formulation becomes more viscous at shear rates from about 2.5sec⁻¹ to about 90 sec⁻¹. More preferably, the lip gloss formulationbecomes more viscous at shear rates from about 5 sec⁻¹ to about 80sec⁻¹. Most preferably, the lip gloss formulation becomes more viscousat shear rates from about 10 sec⁻¹ to about 70 sec⁻¹.

The viscoelastic properties may be characterized, for example, by a losstangent, tan(δ) which is substantially linear or smooth over the widestpossible range of shear rates, but exhibits a sharp, discontinuous riseat shear rates typically encountered during application to a selectedsurface. In addition, at shear rates typically encountered during wear,the lip gloss formulation exhibits balanced viscoelastic properties, forexample, having a loss tangent value within a range from about 1 toabout 10. The loss tangent may be substantially linear or smooth andhave a value between about 1 to about 10 at shear rates from about 0.1to about 15 sec⁻¹, preferably from about 0.1 to about 20 sec⁻¹, morepreferably from about 0.1 to about 30 sec⁻¹, and more preferred still,from about 0.1 to about 70 sec⁻¹ . By “substantially linear or smooth”is meant that the curve of G′, G″, or tan(δ) versus shear rate do notexhibit a sharp, discontinuous rise or fall over a given range of shearrates.

EXAMPLE I Lip Gloss

A long-wearing, transfer resistant lip gloss having a synergisticcombination of silicone polyurethane polymer and silicone gum elastomeris provided in Table 1. The lip gloss may be used alone as along-wearing transfer resistant lip gloss, or as a base coat under aclear or tinted top coat. An optional top coat formulation is alsoprovided in Table 1. The optional top coat may be employed to enhanceshine and/or moisturization without substantially removing the basecoat.

TABLE 1 Components Weight % Silicone Polyurethane MR-20-41 (Siltech45.00 Corporation) (40% in IDD) Silicone Gum SE63 (GE Silicones)/IDD(1:2) 10.00 Bentone Gel-IDD/disterardimonium 4.00 PentaerythritylTetra-Di-T-Butyl 0.05 Hydroxyhydrocinnamate Cromapure GDE 1.00 CaprylylGlycol 0.50 Fragrance/Acrylate Copolymer 0.20 Pigment Blend 11.40Isododecane 27.85 Total 100 Optional Top Coat Polybutene 70.00 (filmformer, shine, thickener) Hydrogenated Polyisobutene 26.43 (oil/solvent)Jojoba Oil/Gellants/BHT-Hi Viscosity 3.00 (moisturizer, shine,thickener) Hydroxystearic Acid 0.27 (gelling agent) Benzoic Acid 0.20(preservative) Fragrance (optional) 0.10 Total 100

EXAMPLE II

The effect of adding silicone gum to a lip gloss formulation containinga silicone polyurethane copolymer was investigated in relation to thetransfer resistance of a lip product. Two samples of a lip glossformulation were prepared according to Table 2.

The silicone polyurethane polymer is a commercial product sold under thedesignation MR-20-41 (Siltech Corporation), which is available as asolution in MD at about 40% by weight. Similarly, the silicone gum is acommercial product sold under the trade name SE63 (GE Silicones) andavailable as a solution in IDD at about 50% by weight. Table 2 belowprovides the converted weights representing the weight % of neatsilicone polyurethane copolymer and neat silicone gum in each sampleformulation (i.e., in the absence of IDD).

TABLE 2 Sample Number: 1 2 Components Weight % Silicone PolyurethaneMR-20-41 (Siltech Corp.) 15.0 15.0 Silicone Gum SE63 (GE Silicones) — 8Rhoepearl TT2 2 2 Pigment Blend 10 10 Isododecane q.s. q.s. Total 100100

The water and oil transfer resistances of the lip gloss formulations ofSamples 1 and 2 were examined in comparison to the commercial lipcoloring products Lipfinity™ (Procter & Gamble) and Lip Polish™(Maybelline) using a modification of the transfer resistance testingprotocol of U.S. Pat. No. 6,074,654, the disclosure of which is herebyincorporated by reference. The testing protocol is described below.

Transfer Resistance Test Method

This method may be utilized to determine the water and oil transferresistances and adhesion properties of a cosmetic film. This testpredicts the ability of a cosmetic film to resist color transfer toobjects contacting the skin. Such objects include clothing,handkerchiefs or tissues, napkins and implements such as cups, glassesand table wear, and oily fingers or objects such as oily foods.

Films formed from cosmetic compositions exhibit a degree of transferresistance directly proportional to the hardness and solvent-resistanceof the film. The hardness and solvent-resistance may be expressed as afunction of the blot and rub test as described below.

Equipment:

-   -   (1) Glass plates;    -   (2) Collagen sausage casing such as Nippi Casing F Grade;    -   (3) Constant humidity chamber adjusted to 95% relative humidity;    -   (4) Utility Knife;    -   (5) Ruler;    -   (6) Single-sided adhesive tape;    -   (7) Double-sided adhesive tape;    -   (8) 25 micron thickness slot draw-down bar;    -   (9) White Styrofoam dinner plate such as Amoco Selectables™        Plastic DL® Tableware;    -   (10) 1.5 inch diameter circular metal punch;    -   (11) 1 kilogram weight;    -   (12) Vegetable oil;    -   (13) Brush-tip cosmetic applicator; and    -   (14) Lint-Free Wiper, such as Kimwipes® EX-L.

Procedure:

-   -   (1) Prepare a 3×4 inch sheet of collagen sausage casing by        hydrating it in a 90% relative humidity chamber for at least 24        hours;    -   (2) Remove the collagen sheet to ambient conditions and        immediately wrap tightly around the glass plate. Attach the        collagen sheet to the glass using adhesive tape. The collagen        surface should be flat and free of wrinkles;    -   (3) Allow the collagen-wrapped slide to equilibrate at ambient        conditions for about 24 hours;    -   (4) Apply thin (1 mm), uniform films of a sample cosmetic        composition on the collagen;    -   (5) Allow the cosmetic samples on the collagen surface to rest        at ambient conditions for about one hour;    -   (6) Using a pipette, drop three drops of vegetable oil onto        samples located the right side of the collagen surface. Using        another pipet, drop three drops of water onto the left side of        the collagen surface. Samples on the right side are used to        determine the oil transfer resistance while samples on the left        side are used to determine the water transfer resistance of the        sample cosmetic composition;    -   (7) Separately for the oil and water sections, distribute the        oil or water evenly over the surface of each cosmetic film        sample using cosmetic brush applicators, brushing lightly;    -   (8) Allow the solvent to remain on the film undisturbed for        about 15 minutes;    -   (9) Using a lint-free wiper, carefully blot excess solvent from        the surface of each cosmetic film sample. Apply as little        pressure as possible during this step;    -   (10) Cut two disks from a clean, white Styrofoam dinner plate        using a 1.5 inch diameter circular punch. The surface and edges        of each disk should be smooth and even;    -   (11) Firmly attach with double-sided adhesive tape each disk        from step (10) to the bottom surface of a 1 kg weight;    -   (12) Set the weight on top of the cosmetic samples applied to        the collagen surface from step (5) above so that a first disk is        in contact with the oil section of the film (i.e., the right        side of the collagen surface) and a second disk is in contact        with the water section of the film (i.e., the left side of the        collagen surface). It is important to position the weight gently        so that excess force beyond 1 kg is not applied;    -   (13) Grasping the top of the 1 kg weight, carefully rotate each        disk through 360 degrees while maintaining the 1 kg force on the        film. Do not lift or press the weight into the film during the        rotating motion to the weight. The entire 360 degree rotation is        preferably completed within a time interval between 3 and 5        seconds;    -   (14) Lift the weight straight up off the film surface and        carefully remove the disk from the weight avoiding damage to the        disk;    -   (15) Color transfer on each disk is visually assessed by        comparing disks obtained using commercial products. The        commercial products serve as positive and negative control        benchmarks. The positive control is the Lipfinity™ product and        the negative control is the Lip Polish™ product; and    -   (16) The criteria used in the “Star Grading System” for        measuring the degree of transfer is shown in Table 3.

TABLE 3 Star Grading System Visual Assessment of Transfer Scale Lessthan Negative Control * (1) Equal to or slight better than Negativecontrol ** (2) Between Negative and Positive Control *** (3) About equalto positive control **** (4) Better than positive control ***** (5)

The results indicate that the lip gloss formulations of Example Iexhibit equal or better water and oil transfer resistances than thenegative (Lip Polish™) control. However, only Sample 2 exhibits equal orbetter water and oil transfer resistances than the positive (Lipfinity™)control. The results are quantified on the basis of the Star GradingSystem as shown below in Table 4.

TABLE 4 Transfer Resistance Properties Water Oil Transfer ResistanceTransfer Resistance Sample Number: (Star Grading) (Star Grading) 1 2 3 25 4

The results indicate that the combination of silicone polyurethane andsilicone gum (Sample 1) is superior in water and oil transfer resistanceas compared to silicone polyurethane copolymer alone (Sample 2).Notably, the addition of silicone gum in Sample 2 resulted in a markedimproved water and oil transfer resistance over Sample 1.

EXAMPLE III

Based on the results described in Example II, Samples 3 through 10 wereprepared to investigate the synergistic properties of siliconepolyurethane copolymer and elastomeric materials silicone gum and/orpolyisobutylene). Sample 3 comprises silicone polyurethane in theabsence of elastomers whereas Samples 4 and 5 comprise the twoelastomers in the absence of a silicone polyurethane. Samples 6 through10 comprise various combinations of silicone polyurethane andelastomers.

The silicone polyurethane is a commercially available product sold underthe designation MR-20-41 (Siltech Corporation), which is available inIDD at about 40% by weight. Similarly, the silicone gum SE63 (GESilicones) is also available in IDD at about 33% by weight. Further, thepolyisobutylene is commercially sold under the designation Permethyl 98B(Presperse, Inc.) and available as a 50% solution in IDD. Table 5 belowprovides the converted weights representing the weight % of neatsilicone polyurethane copolymer, neat silicone gum, and/or neatpolyisobutylene in each sample formulation (i.e., in the absence ofIDD).

TABLE 5 Sample Number: 3 4 5 6 7 8 9 10 Components Weight % Silicone18.00 — — 12.00 12.00 6.00 12.00 6.00 Polyurethane MR-20-41 (SiltechCorp.) Silicone Gum — 18.00 — 6.00 — 6.00 3.00 12.00 SE 63 (GESilicones) Permethyl 98B — — 18.00 — 6.00 6.00 3.00 — (Presperse, Inc.)Caprylyl 0.50 0.50 0.40 0.50 0.50 0.50 0.50 0.50 Glycol Tinoguard 0.050.05 0.05 0.05 0.05 0.05 0.05 0.05 Bentone Gel 10.00 10.00 10.00 10.0010.00 10.00 10.00 10.00 Pigment 10.00 10.00 10.00 10.00 10.00 10.0010.00 10.00 Isododecane q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. Total100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00

It was observed that the lip gloss formulation having 18% by weightsilicone polyurethane copolymer in the absence of any elastomer (i.e.,Sample 3) was a relatively unstable formulation and demonstrated phaseseparation. To minimize the potential for experimental error (i.e.,phase separation of the formulation biasing the measurements obtainedusing the transfer resistance test) and to improve the reliability ofthe results, two identical samples (Samples 3A and 3B) of thisformulation were prepared.

In contrast to what was observed for Sample 1 of Example II, Sample 3Aprovided relatively high oil transfer resistance, showing a Star Gradingof 4, but provided an unusually high water transfer resistance, giving aStar Grading of 5. It is believed that this result is spurious as phaseseparation was clearly visible in Sample 3A prior to transfer resistancemeasurements, which compromised the accuracy and reliability of thetransfer resistance test. Measurements generated using Sample 3A were,therefore, discarded.

The remainder of the measurements were conducted using Sample 3B, whichdid not suffer from phase separation. The water and oil transferresistance test was repeated nine times for Sample 3B. The nine watertransfer resistance tests yielded of 2, five measurements of 3 and onemeasurement of 4 on the Star Grading System. The nine oil transferresistance tests gave two measurements of 3, five measurements of 4 andtwo measurements of 5. The transfer resistance data for Sample 3, asshown in Table 6 and discussed below, is represented by the meantransfer resistance of the nine tests of Sample 3B.

The water and oil transfer resistance properties of Samples 4 through 10were also obtained using the method described in Example II. Thesesamples did not visibly show any phase separation during the transferresistance tests. The results for Samples 4 through 10 are quantified onthe basis of the Star Grading System as shown below in Table 6.

TABLE 6 Transfer Resistance Properties Water Oil Transfer ResistanceTransfer Resistance Sample Number: (Star Grading) (Star Grading)  3¹ 2.84 4 4 1 5 1 2 6 5 5 7 3 5 8 5 4 9 5 5 10  5 3 ¹Sample 3 is representedby the average Star Grading value of the 9 transfer resistance tests forSample 3B.

The results indicate that silicone polyurethane polymer and silicone gumin lip gloss formulations act synergistically to impart water transferresistance. As shown in Table 6, the combination of siliconepolyurethane and silicone gum in Samples 6 and 10 are superior on thebasis of water transfer resistance to both Samples 3 and 4, which do notinclude this synergistic combination. Both Samples 6 and 10 provide aStar Grading of 5 for water transfer resistance whereas Sample 3 showsan inferior Star Grading of 2.8 and Sample 4 shows a modestly inferiorStar Grading of 4 for water transfer resistance.

The results also demonstrate that the combination of siliconepolyurethane polymer, silicone gum, and polyisobutylene synergisticallyimproves water transfer resistance. As shown in Table 6, Samples 8 and 9were found to be superior on the basis of water transfer resistance toSamples 3, 4 and 5, which do not include this synergistic combination.Both Samples 8 and 9 exhibit the Star Grading of 5 for water transferresistance whereas Sample 3, 4, and 5 show inferior Star Gradings of2.8, 4 and 1, respectively.

The results also clearly show that silicone polyurethane polymer andpolyisobutylene in lip gloss formulations act synergistically to impartoil transfer resistance. Sample 7 which comprises a combination ofsilicone polyurethane and polyisobutylene gives superior oil transferresistance as compared to Sample 3, which comprises siliconepolyurethane but no elastomer, and Sample 5, which comprisespolyisobutylene but no silicone polyurethane. Notably, Sample 7 providesa superior Star Grading of 5 for oil transfer resistance as compared tothe oil transfer resistance of Samples 3 and 5.

During normal wear conditions, a lip gloss formulation may be exposed toboth aqueous and oily conditions. Often, the lip gloss formulation maybe exposed to both water and oil at or about the same time, such as, forexample, during the consumption of food and beverage. To predict theoverall ability of a cosmetic film to resist color transfer to objectscontacting the skin under normal wear conditions, which includesexposure to both water and oil, lip gloss formulations may also beevaluated using a parameter for combined transfer resistance, which isdefined by the sum of the water transfer resistance and the oil transferresistance of each sample.

The combined transfer resistance of Samples 3 through 10 were obtainedby summing the water transfer resistance and the oil transfer resistanceof each sample. The combined transfer resistance for Sample 3 wasobtained by the sum of the average water transfer resistance and theaverage oil transfer resistance of nine transfer resistance testsdescribed previously. The combined transfer resistance for Samples 3through 10 are provided on the basis of the Star Grading System as shownbelow in Table 7.

TABLE 7 Sample Number: Combined Transfer Resistance  3¹ 6.8 4 5 5 3 6 107 8 8 9 9 10 10  8 ¹Sample 3 is represented by the average Star Gradingvalue of 9 transfer resistance tests for Sample 3B.

The results show that the combination of silicone polyurethane polymerand elastomer in a tip gloss formulation synergistically impartstransfer resistance based on the combined transfer resistance parameter.As shown in Table 7, Samples 6 through 10, which comprises a combinationof silicone polyurethane with at least one elastomer, exhibit overallsuperiority based on the combined transfer resistance as compared toSamples 3, 4 and 5, which do not include such combination.

EXAMPLE IV

Samples 11 through 17 were prepared to investigate the effect ofdifferent amounts of silicone polyurethane on the transfer resistance ofa lip product. The silicone polyurethane polymer for Samples 11 through17 is the same as the silicone polyurethane polymer listed in ExampleIII, which is a commercial product sold under the designation MR-20-41(Siltech Corporation) and available as a solution in IDD at about 60% byweight. Table 8 below provides the converted weights representing theweight % of neat silicone polyurethane copolymer in each sampleformulation (i.e., in the absence of IDD).

TABLE 8 Sample Number: 3 11 12 13 14 15 16 17 Components Weight %Silicone 18.00 16.00 14.00 12.00 10.00 8.00 6.00 4.00 PolyurethaneMR-20-41 (Siltech Corp.) Silicone Gum — — — — — — — — SE 63 (GESilicones) Permethyl 98B — — — — — — — — (Presperse, Inc.) Caprylyl 0.500.50 0.50 0.50 050 0.50 0.50 0.50 Glycol Tinoguard 0.05 0.05 0.05 0.050.05 0.05 0.05 0.05 Bentone Gel 10.00 10.00 10.00 10.00 10.00 10.0010.00 10.00 Pigment 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00Isododecane q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. Total 100.00 100.00100.00 100.00 100.00 100.00 100.00 100.00

The water and oil transfer resistance properties were obtained using themethod described in Example II. These samples also did not visibly showany phase separation during the transfer resistance tests. The combinedtransfer resistance, as defined above in Example III, were obtained bycalculating the sum of the water transfer resistance and the oiltransfer resistance of each sample. The results for Samples 11 through17 are quantified on the basis of the Star Grading System as shown belowin Table 9.

TABLE 9 Transfer Resistance Properties Sample Water Transfer OilCombined Number: Resistance Transfer Resistance Transfer Resistance  3¹2.8 4 6.8 11 3 4 7 12 3 4 7 13 3 4 7 14 3 3 6 15 3 3 6 16 3 2 5 17 3 1 4

Interestingly, the water transfer resistance appears to be independentof silicone polyurethane concentration, yielding a value of about 3 StarRating units across a greater than 4-fold concentration range. Incontrast, the dose-response for oil transfer resistance increased at lowconcentration, then plateaus above 10% by weight.

Samples 18 through 20 were prepared to investigate the effect ofdifferent amounts of silicone polyurethane, in the presence of siliconegum, to the transfer resistance of a lip product. The siliconepolyurethane polymer for Samples 18 through 20 is the same as thesilicone polyurethane used for Samples 3 through 17. All materials usedin the formulations in Table 10 are the same as previously described andall weights represent the weight percent of neat materials.

TABLE 10 Sample Number: 4 6 18 19 20 10 Components Weight % Silicone —12.00 8.00 6.00 4.00 6.00 Polyurethane MR-20-41 (Siltech Corp.) SiliconeGum 18.00 6.00 6.00 6.00 6.00 12.00 SE 63 (GE Silicones) Permethyl 98B —— — — — — (Presperse, Inc.) Caprylyl 0.50 0.50 0.50 0.50 0.05 0.50Glycol Tinoguard 0.05 0.05 0.05 0.05 0.05 0.05 Bentone Gel 10.00 10.0010.00 10.00 10.00 10.00 Pigment 10.00 10.00 10.00 10.00 10.00 10.00Isododecane q.s. q.s. q.s. q.s. q.s. q.s. Total 100.00 100.00 100.00100.00 100.00 100.00

The water and oil transfer resistance properties were obtained using themethod described in Example II. The combined transfer resistance, asdefined above, was obtained by summing the water transfer resistance andthe oil transfer resistance for each sample. The results, quantified onthe basis of the Star Grading System, are shown below in Table 11.

TABLE 11 Transfer Resistance Properties Sample Water Transfer OilCombined Number: Resistance Transfer Resistance Transfer Resistance 4 41 5 6 5 5 10 18 4 4 8 19 4 4 8 20 4 2 6 10 5 3 8

FIG. 1 illustrates the water transfer resistance of lip glossformulations comprising silicone polyurethane in the absence of anelastomer, e.g., lip gloss formulations provided in Table 8 (Samples 3and 11-17), with the symbol (♦) as a function of the amount of siliconepolyurethane (by weight %). The water transfer resistance of lip glossformulations comprising different concentrations of siliconepolyurethane with 6 weight % silicone gum is represented by the symbol(▪). As can be seen, the water transfer resistance curve of (▪) is abovethe water transfer resistance curve of (♦) at all data points, furtherdemonstrating that the addition of silicone gum improves the watertransfer resistance of a lip gloss formulation comprising a siliconepolyurethane copolymer. The water transfer resistance for a lip glossformulation comprising silicone polyurethane and 12% by weight siliconegum (Sample 10), as shown with the symbol (▴) in FIG. 1, also lies abovethe water transfer resistance curve of (♦), further illustrating thisbroad synergy. The water transfer resistance for Sample 4 comprisingsilicone gum in the absence of silicone polyurethane polymer is alsoillustrated in FIG. 1 by a dotted line. This dotted line is provided forcomparison but does not represent the water transfer resistance ofsamples including silicone polyurethane.

The dose-response curve of the samples of Table 8, represented by (♦),shows that water transfer resistance of the lip gloss formulationscomprising silicone polyurethane in the absence of elastomer isindependent of the amount of silicone polyurethane present acrosssilicone polyurethane concentrations from about 4 weight % to about 18weight %, each concentration giving a Star Grading of 3 except forSample 3, which is nevertheless very close to 3 (average Star Grading2.8). As discussed above, the relative instability of the lip glossformulation at 18% by weight silicone polyurethane, alone, likely givesrise to the minor experimental deviation observed for this sample, butis not considered to be significant.

The results show that lip gloss formulations comprising siliconepolyurethane and silicone gum at ratios of 1:2 and 2:1 demonstrate asynergistic improvement in water transfer resistance. Notably, Sample 6(▪), which includes silicone polyurethane and silicone gum in a ratio of2:1, and Sample 10 (▴), which includes silicone polyurethane andsilicone gum in a ratio of 1:2, both show a superior Star Grading of 5as compared to lip gloss formulations of Table 8 (♦), and the watertransfer resistance for a lip gloss formulation comprising 18 weight %silicone gum as represented by the horizontal dotted line at amoderately inferior Star Grading of 4.

FIG. 2 illustrates the oil transfer resistance of lip gloss formulationsof Table 8 and Table 10 as a function of silicone polyurethaneconcentration. Lip gloss formulations comprising varying amounts ofsilicone polyurethane (without elastomer) are represented by the symbol(♦), and formulations comprising varying amounts of siliconepolyurethane with 6 weight % silicone gum are represented by the symbol(▪). The water transfer resistance for Sample 10, which comprisessilicone polyurethane and 12% silicone gum, is shown with the symbol(▴). The oil transfer resistance for Sample 4 is illustrated with adotted line as an exemplary lip gloss formulation comprising siliconegum in the absence of silicone polyurethane polymer.

The results suggest that silicone polyurethane polymer and silicone gumin lip gloss formulations act synergistically to impart oil transferresistance. The oil transfer resistance curve (♦) steadily increases atsilicone polyurethane concentrations from 4 weight % to 12 weight % andat silicone polyurethane concentrations above 10 weight %, morespecifically at silicone polyurethane concentrations between 12 weight %to 18 weight %, the oil transfer resistance curve plateaus to a StarGrading of 4. As can be seen in FIG. 2, the oil transfer resistancecurve of the synergistic combination (▪) lies above the oil transferresistance curve of silicone polyurethane alone (♦) for all data pointsand is also above the oil transfer resistance for 18 weight % siliconegum (dotted line). Notably, at 12 weight % silicone polyurethane, thesynergistic combination (▪) has a Star Grading of 5, surpassing the oiltransfer resistance observed in lip gloss formulations comprisingsilicone polyurethane in the absence of an elastomer (♦), whichincreases at low concentrations of silicone polyurethane but plateaus ata moderate Star Grading of 4. Similarly, Sample 10 (▴) is superior onthe basis of oil transfer resistance as compared to: (1) the lip glossformulations of Table 8 (♦); and (2) Sample 4, as represented by thehorizontal dotted line at the minimum possible Star Grading of 1.

FIG. 3 illustrates the combined transfer resistance of tip glossformulations of Tables 8 and 10 as a function of silicone polyurethaneconcentration where the lip gloss formulations comprising siliconepolyurethane but no elastomer of Table 8 are represented with the symbol(♦) and lip gloss formulations of Table 10 comprising siliconepolyurethane and 6 weight % silicone gum are represented by the symbol(▪). Sample 10, which comprises silicone polyurethane and 12 weight %silicone gum is illustrated with the symbol (▴) in FIG. 3. The combinedtransfer resistance for Sample 4 comprising silicone gum in the absenceof silicone polyurethane polymer is illustrated with a dotted line.

The combined transfer resistance curve (♦) steadily increases atsilicone polyurethane concentrations from 4 weight % to 12 weight %. Atsilicone polyurethane concentrations between 12 weight % to 18 weight %,the oil transfer resistance curve plateaus to about a Star Grading of 7.As shown in FIG. 3, at 18 weight % (Sample 3), the combined transferresistance of (♦) diverges slightly below the Star Grading of 7 whereasother samples above 12 weight % (Samples 11-13) show a Star Grading of 7although this difference is not considered significant.

The results suggest that silicone polyurethane polymer and silicone gumin lip gloss formulations act synergistically to impart transferresistance on the basis of the combined parameter of oil and watertransfer resistance. The addition of silicone gum to lip glossformulations comprising silicone polyurethane provides overallsuperiority based on the combined parameters of water transfer and oiltransfer resistance as compared to lip gloss formulations without thesynergistic combination of the present invention. As shown in FIG. 3,the combined transfer resistance curve (▪) lies above the combinedtransfer resistance curve (♦) for all data points and is also above thecombined transfer resistance for 18 weight % silicone gum (Sample 4) asrepresented by the dotted line. In particular, at and above 6 weight %silicone polyurethane, the combined transfer resistance curve (▪)surpasses the combined transfer resistance observed for lip glossformulations comprising silicone polyurethane in the absence of anelastomer (♦). Similarly, Sample 10 (▴) is superior on the basis ofcombined oil and water transfer resistance as compared to lip glossformulations of Table 8 (♦) and Sample 4 (dotted line).

EXAMPLE V Frequency Sweep Rheology Test

The viscoelastic properties, which quantify the flow and deformationbehaviors were examined for (A) silicone polyurethane, (B) silicone gum,(C) polyisobutylene, (D) silicone polyurethane with silicone gum, and(E) silicone polyurethane with polyisobutylene using a frequency sweeprheology test. The frequency sweep rheology test examines the effect ofshear frequency or shear rate on the microstructural properties of amaterial through the response of the material to a range of shear rates.Specifically, the frequency sweep rheology test described below measuresthe storage modulus (G′) and the loss modulus (G″) as a function ofshear rates.

A Paar Physica USD200 Universal rotational rheometer was used to measurethe storage modulus (G′) and the loss modulus (G″) of each sample. Thestorage modulus (G′) and the loss modulus (G″) for each sample wasmeasured at different shear rates varying from 0.1 sec⁻¹ to 100 sec⁻¹.The measurements were obtained using a cone-and-plate geometry, whereeach sample is placed onto a fixed plate of the rheometer while amoveable cone is brought into contact with the sample and applies ashear to the sample. Each samples is maintained at a temperature of 33°C. as the storage modulus (G′) and the loss modulus (G″) are measured atdifferent shear rates.

A frequency sweep test measuring the storage modulus (G′) was conductedfor compositions of silicone polyurethane MR-20-41 (Siltech Corporation)(40 weight % in IDD) (A), silicone gum SE63 (GE Silicones) (50 weight %in IDD) (B), and polyisobutylene Permethyl 98B (Presperse, Inc.) (50weight % in IDD) (C). The frequency sweep test was also conducted formixed compositions of silicone polyurethane (22.2 weight %) withsilicone gum (22.2 weight %) in IDD (D) and silicone polyurethane (22.2weight %) with polyisobutylene (22.2 weight %) in IDD (E). The resultsof the frequency sweep test for the storage modulus (G′) and the tosstangent (tan δ) of these compositions are illustrated as a function ofthe frequency, or shear rate, in FIGS. 4 and 5, respectively. At highshear rates, the loss tangent (tan δ) appears to plateau at about 10⁶,but this is merely a limitation of the rheometer used and represents themaximum loss tangent measurable at these values. In actuality, the losstangent will have the shape of a tangent function, with a verticalasymptote.

Polydimethylsiloxane polyurethane does not have balanced viscoelasticproperties because, while it is highly viscous, it is poorly elastic.FIG. 4 shows the G′ storage modulus of a representativepolydimethylsiloxane polyurethane, silicone polyurethane MR-20-41(Siltech Corporation) (40 weight % in IDD) (A), as a function of shearrate in inverse seconds. As can be seen in FIG. 4, the G′ storagemodulus for silicone polyurethane (A) breaks down sharply at low shear(below 1 sec⁻¹) which indicates that even at low shear rates the polymerhas little elasticity but high viscosity. The sharp drop in G′ storagemodulus for this material is due to the dissipation of the stored energyto the system in the form of heat owing to the viscous nature of thepolymer. In other words, at low shear rates, the loss modulus G″ becomesvery large.

The elastomers are by definition highly elastic and thus, arecharacterized by a G′ storage modulus that is relatively steady orincreasing over a wide range of shear rates, for example from shearrates of 0.1 to 50 sec⁻¹ or from 0.1 to 100 sec⁻¹ or even higher. Theelastomers do not exhibit a break down in G′ storage modulus at lowshear rates as seen with the polyorganosiloxane polyurethane polymer(A). Rather, elastomers maintain relatively steady values for the G′storage modulus over a wide range of shear rates. The G′ storage modulusfor an exemplary silicone gum elastomer, SE63 (GE Silicones) (50 weight% in IDD) (B), remains highly elastic over broad range of shear rages,including and beyond 100 sec⁻¹. Another example of an elastomer is apolyisobutylene Permethyl 98B (Presperse, Inc.) (50 weight % in IDD)(C), which remains highly elastic over a broad range of shear rates andthe G′ storage modulus break down only at shear rates approaching 100sec⁻¹.

The inclusion of elastomers in the cosmetic composition imparts anelastic component to balance the viscosity of the polyorganosiloxanepolyurethane polymer, providing a cosmetic composition having idealviscoelastic properties. As seen in FIG. 4, the exemplary mixedcompositions (D and E) comprising silicone polyurethane and elastomerdemonstrate relatively linear storage modulus (G′) at low shear rates(from about 0.1 to about 10 sec⁻¹), corresponding to the range of shearrates typically encountered during wear, and begin to break down atshear rates between about 10 to about 100 sec⁻¹, which correspond to arange of shear forces typically encountered during application of thecosmetic composition to the skin. Accordingly, the mixed compositionsbegin to transition from having balanced viscoelastic properties tohaving predominantly viscous properties at these higher shear rates andthus exhibit beneficial viscoelastic properties at shear forcestypically encountered during wear but allow for excellent pay-off duringapplication of cosmetic. As demonstrated in FIG. 5, the exemplary mixedcompositions (D and E) also demonstrate desirable viscoelasticproperties, as quantified by having a loss tangent value between about 1to about 10, for low shear rates and a sharp, discontinuous riseoccurring at a shear rates between about 10 to about 100 sec⁻¹.

EXAMPLE VI

Cosmetically optimized lip gloss formulations, Samples 21 through 25,were prepared according to the formulations shown in Table 12, whichprovides the converted weights representing the weight % of neatsilicone polyurethane copolymer, neat silicone gum, and/or neatpolyisobutylene in each sample formulation (i.e., in the absence ofIDD). Samples 21 and 25 comprises elastomer but not siliconepolyurethane copolymer. Samples 23 and 24 comprise 18.00% by weight ofsilicone polyurethane polymer and either 9.33% by weight of silicone gumor 14.00% by weight of polyisobutylene, respectively. Sample 22comprises a combination of silicone polyurethane copolymer, silicone gumand polyisobutylene.

TABLE 12 Sample Number: 21 22 23 24 25 Components Weight % SiliconePolyurethane — 17.60 18.00 18.00 — MR-20-41 (Siltech Corp.) Silicone GumSE 63 (GE 20.00 5.00 9.33 — — Silicones) Permethyl 98B — 7.50 — 14.0025.00 (Presperse, Inc.) Caprylyl Glycol — 0.50 0.50 0.50 0.50 Tinoguard— 0.05 0.05 0.05 0.05 Bentone Gel 6.00 5.00 5.00 5.00 10.00 DowCorning ® — 1.00 1.00 1.00 — 9701 cosmetic powder Jetmilled Pigment10.00 11.00 11.00 11.00 12.00 Isododecane q.s. q.s. q.s. q.s. q.s. Total100.00 100.00 100.00 100.00 100.00

The water and oil transfer resistance properties were obtained using themethod described in Example II. The results for Samples 21 through 25are also quantified on the basis of the Star Grading System as shownbelow in Table 13.

TABLE 13 Transfer Resistance Properties Water Oil Sample Number:Transfer Resistance Transfer Resistance 21 2 5 22 5 3 23 5 4 24 4 3 25 25

A frequency sweep test measuring the storage modulus (G′) and lossmodulus (G″) was conducted for Sample 1 from Example 1 and Samples 11through 15. The results of the frequency sweep test for the storagemodulus (G′) and the loss tangent (tan δ) of these compositions areillustrated as a function of the shear rate in FIGS. 6 and 7,respectively.

The cosmetically optimized lip gloss formulations begin to transitionfrom having elastic properties to having viscous properties above shearrates typically encountered during wear, about 0.1 to about 10 sec⁻¹,for all samples except Sample 1, indicating that the formulations havedesirable viscoelastic properties and consequently greater substantivityto the skin. As shown in FIG. 6, Sample 22 demonstrate relatively linearstorage modulus (G′) at tow shear rates (from about 0.1 to about 10sec⁻¹), corresponding to the range of shear rates typically encounteredduring wear, but begins to break down at a shear rate about 22 sec⁻¹,which is within a range of shear forces typically required forapplication of the cosmetic composition to the skin. Sample 23 and 24also show relatively linear storage modulus at low shear rates, andbegin to break down at shear rates about 32 sec⁻¹ and about 15 sec⁻¹,respectively. Thus, the lip gloss formulations having the synergisticcombination of the invention (Samples 22-24) are expected to possessgood substantivity to the skin during wear but also will be easy toapply. As demonstrated in FIG. 7, the cosmetically optimized lip glossformulations having the synergistic combination (Samples 22, 23 and 24)also demonstrate desirable viscoelastic properties, as quantified byhaving a loss tangent value between about 1 to about 10, for low shearrates of about 0.1 sec⁻¹ to about 5, 6, 7, 8, 9, 10 sec⁻¹ and begin toexhibit a sharp, discontinuous rise at shear rates about 22 sec⁻¹, about32 sec⁻¹, and about 15 sec⁻¹, respectively. These beneficialviscoelastic properties are believed to contribute to the superior watertransfer resistance for Samples 22, 23 and 24 which give a Star Gradingof 5, 5, and 4, respectively, in contrast to the inferior Star Gradingof 2 for Samples 21 and 25, which do not include the synergisticcombination of the present invention.

Film Flexibility Test

The flexibility of Samples 22-25 were examined using a modification ofthe flexibility testing protocol described in patent U.S. Pat. No.6,074,654, the contents of which are hereby incorporated by reference.The flexibility of a cosmetic film is important to both the durability(long-wear) and comfort properties of a cosmetic film.

Flexibility is measured by the latex stretch test. This test predictsthe ability of the color film to resist flaking or peeling types offailure after application by movement of the skin during normalactivities. The flexibility latex stretch test is based on theweight-loss measurement before and after the latex stretch.

Equipment:

-   -   (1) Ansell industrial technicians unlined gloves (12″ length, 17        mil) USDA Accepted #390, Size 9;    -   (2) Slanted Eyeshadow Brushes from Avon Products, Inc.    -   (3) Analytical balance (4 decimal places); and    -   (4) Ruler.

Procedure:

-   -   (1) Cut a 1 inch wide band from the wrist area of the glove,        avoiding the ribbing and thumb.    -   (2) Mark off a 1×1 inch block in the center of smooth side of        the band, avoiding the embossed number.    -   (3) Weigh and record the weight of the latex band; hereinafter        referred to as A.    -   (4) Determine the initial weight of the cosmetic to be applied        to the band in order to produce a dried film weighing 20 mg.        This is determined by dividing 20 mg by the weight percent of        non-volatile material present in the cosmetic. For example, 40        mg of a cosmetic with 50% non-volatile content must be applied        to the hand in order to yield a 20 mg dried film.    -   (5) Using a clean eyeshadow brush, evenly apply the amount of        cosmetic determined in step (4) over the 1×1 inch area of the        band as marked in step (2).    -   (6) Immediately weigh and record the combined weight of the        latex band and applied cosmetic. The weight of wet film with the        latex band is referred to as B.    -   (7) Allow the sample on the latex band from step (6) to sit at        ambient room conditions for one hour.    -   (8) Weigh and record the combined weight of the latex band A and        the applied cosmetic film; hereinafter referred to as C.        Subtract A from C to determine the dried film weight D(D=C−A).        This weight should be 20±2 mg.    -   (9) Gently stretch the latex band so that the marked film length        changes from 1.00 inches to 1.75 inches.    -   (10) Upon observing loosened film pieces on the latex band,        remove the film pieces from the latex band by vigorously wiping        a clean eyeshadow brush across the surface of the film: 10 times        wiping in vertical direction and 10 times wiping in horizontal        direction.    -   (11) Carefully allow the latex band to return to its approximate        original shape.    -   (12) Record the weight of the latex band (with the remaining        cosmetic); herein referred to as E.    -   (13) A “Star Grading System” is used based on percentage weight        loss (“PWL”) to grade the flexibility of the films as follows:

TABLE 14 Flexibility Star Grading System Weight Loss Scale 100-50%  *30-50% ** 15-30% ***  5-15% **** 0-5% *****

The percent weight loss of the cosmetic film is calculated using thefollowing equation:

Percent Weight Loss (PWL)=[1−(E−A)/(C−A)]×100%

For some very flexible films, the percentage weight loss may benegligible. Therefore, in some case, due to some dust transferred fromthe brush, the PWL value may become negative (weight gain).

Steps (1) through (12) are repeated three times for each cosmeticformulation tested. The average of the three PWL values is determined;herein referred to as Average Percent Weight Loss (“APWL”). Low APWLvalues (i.e., 0-5%) correspond to flexible films having a desirableadhesive and cohesive balance of the film. The flexibility test resultsfor Samples 22-25 are quantified on the Star Grading System as shown inTable 15.

TABLE 15 Sample Number: Flexibility Star Grading 22 ***** 23 ***** 24***** 25 *****

All patents and patent publications referred to herein are herebyincorporated by reference.

Certain modifications and improvements will occur to those skilled inthe art upon a reading of the foregoing description. It should beunderstood that all such modifications and improvements have beendeleted herein for the sake of conciseness and readability but areproperly within the scope of the following claims.

1.-27. (canceled)
 28. A cosmetic composition comprising a synergisticcombination of: (i) a silicone polyurethane polymer; and (ii) anelastomeric component comprising a polyorganosiloxane gum having aviscosity of from about 1,000,000 centistokes to about 3,500,000centistokes when measured at 25° C.; wherein the elastomeric componentcomprises one or more elastomers selected from the group consisting ofsilicone gums, polyisobutylene, natural rubbers, and block-copolymerrubbers; wherein the synergistic combination comprises a weight ratio ofsilicone polyurethane polymer to elastomeric component from about 50:1to about 1:50; and wherein the synergetic combination provides animprovement in one or more characteristic selected from the groupconsisting of water transfer resistance, oil transfer resistance,durability, and rheology.
 29. The cosmetic composition of claim 28wherein the synergistic combination comprises a weight ratio of siliconepolyurethane polymer to elastomeric component from about 25:1 to about1:25.
 30. The cosmetic composition of claim 28 wherein the synergisticcombination comprises a weight ratio of silicone polyurethane polymer topolyorganosiloxane gum from about 10:1 to about 1:10.
 31. The cosmeticcomposition of claim 28 wherein the synergistic combination comprises aweight ratio of silicone polyurethane polymer to polyorganosiloxane gumfrom about 5:1 to about 1:5.
 32. The cosmetic composition of claim 28wherein the synergistic combination comprises a weight ratio of siliconepolyurethane polymer to polyorganosiloxane gum from about 3:1 to about1:3.
 33. The cosmetic composition of claim 28 wherein the synergisticcombination comprises a weight ratio of silicone polyurethane polymer topolyorganosiloxane gum from about 2:1 to about 1:2.
 34. The compositionof claim 28 wherein the improvement is selected from the groupconsisting of water transfer resistance and oil transfer resistance. 35.The composition of claim 28 wherein the improvement is an improvement inwater transfer resistance.
 36. The composition of claim 28 wherein thecomposition is one of a lip gloss, a mascara, or a hair care product.37. A method for imparting a transfer resistant film to a biologicalsurface comprising: applying to the surface a composition comprising asynergistic combination of (i) a silicone polyurethane polymer; and (ii)an elastomeric component comprising a polyorganosiloxane gum having aviscosity of from about 1,000,000 centistokes to about 3,500,000centistokes when measured at 25° C.; wherein the elastomeric componentcomprises one or more elastomers selected from the group consisting ofsilicone gums, polyisobutylene, natural rubbers, and block-copolymerrubbers; wherein the synergistic combination comprises a weight ratio ofsilicone polyurethane polymer to elastomeric component from about 50:1to about 1:50; wherein the synergetic combination provides animprovement in one or more characteristic selected from the groupconsisting of water transfer resistance, oil transfer resistance,durability, and rheology; and wherein the composition provides improvedoil and/or water transfer resistance as compared to an otherwiseidentical composition in the absence of either the silicone polyurethanepolymer or the elastomer.
 38. The method of claim 37, wherein theimproved transfer resistance comprises improved water transferresistance.
 39. The method of claim 37, wherein the improved transferresistance comprises improved oil transfer resistance.
 40. The method ofclaim 37, wherein the at least one elastomer comprises silicone gum. 41.The method of claim 37, wherein the at least one elastomer comprisespolyisobutylene.
 42. The method of claim 37, wherein the synergisticcombination comprises a weight ratio of silicone polyurethane polymer toelastomeric component from about 25:1 to about 1:25.
 43. The method ofclaim 37, wherein the synergistic combination comprises a weight ratioof silicone polyurethane polymer to elastomeric component from about10:1 to about 1:10.
 44. The method of claim 37, wherein the synergisticcombination comprises a weight ratio of silicone polyurethane polymer toelastomeric component from about 5:1 to about 1:5.
 45. The method ofclaim 37, wherein the synergistic combination comprises a weight ratioof silicone polyurethane polymer to elastomeric component from about 3:1to about 1:3.
 46. The method of claim 37, wherein the synergisticcombination comprises a weight ratio of silicone polyurethane polymer topolyorganosiloxane gum from about 2:1 to about 1:2.
 47. The method ofclaim 37, further comprising applying an optionally clear top coat overthe transfer resistant film.